JP2020023699A - Thermosetting resin composition for light reflection and method for producing the same - Google Patents

Abstract

To provide a thermosetting resin composition for light reflection which has high reflectance of from visible light to near ultraviolet light, excellent heat deterioration resistance and tablet moldability after curing and hardly causes the generation of burrs during transfer molding.SOLUTION: There is provided a thermosetting resin composition for light reflection which comprises: an oligomer of (A') at least one epoxy resin selected from the group consisting of a bisphenol A type epoxy resin, a bisphenol type F epoxy resin, a bisphenol S type epoxy resin, a diglycidyl isocyanurate and a diglycidyl isocyanurate, (B') a curing agent containing at least one selected from the group consisting of an acid anhydride curing agent, an isocyanuric acid derivative and a phenol-based curing agent; and a white pigment at least one selected from the group consisting of alumina, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide and inorganic hollow particles.SELECTED DRAWING: Figure 1

Description

  The present invention provides a thermosetting light-reflecting resin composition used for an optical semiconductor device in which an optical semiconductor element and a wavelength conversion means such as a phosphor are combined, an optical semiconductor element mounting substrate using the resin composition, The present invention relates to a semiconductor device and a method for manufacturing the same.

  BACKGROUND ART An optical semiconductor device in which an optical semiconductor element such as an LED (Light Emitting Diode) and a phosphor are combined has advantages such as high energy efficiency and a long life, so that it is used for outdoor displays, portable liquid crystal backlights, and in-vehicle applications. The demand is expanding. As a result, LED devices have become higher in luminance, and there has been a problem that the junction temperature rises due to an increase in the amount of heat generated by the elements, or the heat resistance deterioration and light resistance deterioration of the material due to a direct increase in light energy. Patent Literature 1 discloses an optical semiconductor element mounting substrate having excellent light reflection characteristics after a heat resistance test.

JP 2006-140207 A

  However, when a substrate for mounting an optical semiconductor element is manufactured by transfer molding using the thermosetting light-reflecting resin composition disclosed in Patent Document 1, the composition is placed in a gap between an upper mold and a lower mold of a molding die. There is a problem that bleeding and resin burr are easily generated. When the burrs are generated, the burrs protrude into the openings (recesses) in the optical semiconductor element mounting area, which becomes an obstacle when mounting the optical semiconductor element. Further, even if the optical semiconductor element can be mounted, it becomes an obstacle when the optical semiconductor element and the metal wiring are electrically connected by a known method such as a bonding wire. When such a failure occurs, a step of removing burrs is required in the manufacturing process of the optical semiconductor element mounting substrate, and the cost and the manufacturing time are lost.

  The present invention has been made in view of the above, and after curing, has a high reflectance from visible light to near-ultraviolet light, is excellent in heat deterioration resistance and tablet moldability, and is hard to generate burrs during transfer molding. It is an object of the present invention to provide a resin composition for reflective light, a substrate for mounting an optical semiconductor element, an optical semiconductor device using the resin composition, and a method for manufacturing these.

  That is, the present invention is characterized by the following items (1) to (16).

  (1) Thermosetting light reflecting resin containing (A) an epoxy resin, (B) a curing agent, (C) a curing accelerator, (D) an inorganic filler, (E) a white pigment, and (F) a coupling agent. A composition, wherein the molding temperature is 100 ° C. to 200 ° C., the molding pressure is 20 MPa or less, the burr length generated when performing transfer molding under the conditions of 60 to 120 seconds is 5 mm or less, and the wavelength after thermal curing is 350 nm or more. A thermosetting resin composition for light reflection, having a light reflectance at 800 nm of 80% or more.

  (2) As the epoxy resin (A), at least an epoxy resin (A ′) and a curing agent (B ′) are kneaded, and the viscosity at 100 to 150 ° C. is in the range of 100 to 2500 mPa · s. (4) The thermosetting resin composition for light reflection according to the above (1), wherein an oligomer is used.

  (3) The compounding ratio of the (A) epoxy resin and the (B) curing agent is such that the (B) curing agent capable of reacting with the epoxy group per one equivalent of the epoxy group in the (A) epoxy resin. The thermosetting light-reflecting resin composition according to the above (1) or (2), wherein the ratio is such that the number of active groups therein is 0.5 to 0.7 equivalent.

  (4) The thermosetting light-reflecting resin according to any one of (1) to (3), further including a nanoparticle filler having a center particle diameter of 1 nm to 1000 nm as a thickener (H). Composition.

  (5) The inorganic filler (D) is selected from the group consisting of silica, alumina, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, magnesium carbonate, and barium carbonate. The thermosetting light-reflecting resin composition according to any one of (1) to (4), which is at least one selected from the group consisting of:

  (6) The above-mentioned (1), wherein the (E) white pigment is at least one selected from the group consisting of alumina, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide, and inorganic hollow particles. The thermosetting light-reflecting resin composition according to any one of (1) to (5).

  (7) The thermosetting light-reflecting resin composition according to any of (1) to (6), wherein the (E) white pigment has a center particle diameter in a range of 0.1 to 50 μm. object.

  (8) The above (1), wherein the combined amount of (D) the inorganic filler and (E) the white pigment is in the range of 10% by volume to 85% by volume based on the whole resin composition. The resin composition for thermosetting light reflection according to any one of (1) to (7).

  (9) The thermosetting light-reflecting resin composition according to any of (1) to (8), wherein the resin composition is aged at 0 to 30 ° C. for 1 to 72 hours. .

  (10) Any one of the above (1) to (9), wherein the components (A) to (F) are kneaded at a kneading temperature of 20 to 100 ° C. and a kneading time of 10 to 30 minutes. The thermosetting resin composition for light reflection according to 1.

  (11) A method for producing a thermosetting light-reflecting resin composition according to any one of the above (1) to (10), wherein the components (A) to (F) are kneaded, and A method for producing a thermosetting light-reflecting resin composition, comprising a step of thermally aging at 30 ° C. for 1 to 72 hours.

  (12) The method for producing a thermosetting light-reflecting resin composition according to the above (11), wherein the kneading is performed at a kneading temperature of 20 to 100 ° C and a kneading time of 10 to 30 minutes.

(13) A substrate for mounting an optical semiconductor element, comprising the thermosetting resin composition for light reflection according to any one of the above (1) to (10).
(14) An optical semiconductor element mounting substrate having at least one concave portion serving as an optical semiconductor element mounting region, wherein at least an inner peripheral side surface of the concave portion is any one of the above (1) to (10). A substrate for mounting an optical semiconductor element, comprising a light-reflective thermosetting resin composition.

  (15) A method of manufacturing an optical semiconductor element mounting substrate in which at least one concave portion serving as an optical semiconductor element mounting region is formed, wherein at least the concave portion is any one of the above (1) to (10). A method for producing a substrate for mounting an optical semiconductor, characterized by forming the substrate by transfer molding using the thermosetting resin composition for light reflection of (1).

  (16) The substrate for mounting an optical semiconductor element according to (13) or (14) or the substrate for mounting an optical semiconductor element manufactured by the manufacturing method according to (15), and the substrate for mounting an optical semiconductor element. An optical semiconductor device comprising at least an optical semiconductor element mounted on a bottom surface of a concave portion and a phosphor-containing transparent sealing resin layer formed in the concave portion so as to cover the optical semiconductor element.

  According to the present invention, after curing, the reflectance of visible light to near ultraviolet light is high, excellent in heat deterioration resistance and tablet moldability, and, furthermore, a thermosetting light reflection resin composition in which burrs hardly occur during transfer molding and It is possible to provide a substrate for mounting an optical semiconductor element, an optical semiconductor device, and a method for manufacturing the same using the resin composition.

It is a perspective view and a sectional view showing one embodiment of an optical semiconductor element mounting substrate of the present invention. It is the schematic which shows one Embodiment of the process of manufacturing the board | substrate for mounting an optical semiconductor element of this invention. FIG. 2 is a cross-sectional view showing one embodiment of the optical semiconductor device of the present invention. FIG. 4 is a schematic diagram of a mold for burr measurement and resin burr used in an example.

Hereinafter, embodiments of the present invention will be described.
The thermosetting light-reflecting resin composition of the present invention comprises (A) an epoxy resin, (B) a curing agent, (C) a curing accelerator, (D) an inorganic filler, (E) a white pigment, and (F) a cup. It contains a ring agent.

  As the epoxy resin (A), those generally used in epoxy resin molding materials for sealing electronic components can be used, and are not particularly limited. Examples thereof include a phenol novolak epoxy resin and an orthocresol novolak epoxy resin. Epoxidized novolak resins of phenols and aldehydes, including bisphenol A, bisphenol F, bisphenol S, diglycidyl ethers such as alkyl-substituted biphenols, diaminodiphenylmethane, and polyamines such as isocyanuric acid and the reaction of epichlorohydrin. Glycidylamine type epoxy resins, linear aliphatic epoxy resins obtained by oxidizing olefin bonds with a peracid such as peracetic acid, and alicyclic epoxy resins. These may be used alone or in combination of two or more. GoodThe epoxy resin used is preferably relatively non-colored. Examples of such an epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, and diglycidyl isocyanate. Nurate and triglycidyl isocyanurate can be mentioned.

  The epoxy resin (A) contains at least (A ') an epoxy resin and (B') a curing agent, and if necessary, further (C ') a curing accelerator, and has a viscosity at 100 to 150 ° C. (G) oligomer having a range of 100 to 2500 mPa · s is preferably used. The (A ′) epoxy resin, the (B ′) curing agent, and the (C ′) curing accelerator are the same as the (A) epoxy resin, (B) curing agent, and (C) curing accelerator in the present invention. Similar ones can be used.

  The (G) oligomer is, for example, the (A ′) epoxy resin and the (B ′) curing agent, which are capable of reacting with the epoxy group with respect to one equivalent of the epoxy group in the (A ′) epoxy resin. B ′) It can be obtained by blending the active group (acid anhydride group or hydroxyl group) in the curing agent so as to be 0.3 equivalent or less and kneading it until it becomes clay-like. The solid composition is aged at a temperature in the range of 25-60 <0> C for 1-6 hours. When (C ′) a curing accelerator is blended, the amount of the curing accelerator should be 0.005 to 0.05 parts by weight based on 100 parts by weight of the total of (A ′) epoxy resin and (B ′) curing agent. Mix. From the viewpoint of suppressing the burr generation of the resin composition of the present invention, the oligomer (G) thus produced preferably has a viscosity at 100 to 150 ° C in the range of 100 to 2500 mPa · s, and at 100 ° C. More preferably, the viscosity is in the range of 100 to 2500 mPa · s. (G) If the viscosity of the oligomer is less than 100 mPa · s, burrs are likely to occur during transfer molding, and if it exceeds 2500 mPa · s, the fluidity during molding is reduced and moldability is poor. Further, the (G) oligomer can be pulverized until its particle diameter becomes 1 mm or less and stored in an environment at a temperature of 0 ° C. or less, whereby the increase in viscosity can be suppressed or stopped. In addition, about a grinding method, you may use any well-known methods, such as using a porcelain mortar.

  The curing agent (B) can be used without any particular limitation as long as it reacts with the epoxy resin, but is preferably relatively uncolored. Specifically, an acid anhydride curing agent, an isocyanuric acid derivative, a phenolic curing agent, or the like can be used. Examples of the acid anhydride-based curing agent include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, glutaric anhydride. Acid, dimethylglutaric anhydride, diethylglutaric anhydride, succinic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and the like. Examples of isocyanuric acid derivatives include 1,3,5-tris (1-carboxy) Methyl) isocyanurate, 1,3,5-tris (2-carboxyethyl) isocyanurate, 1,3,5-tris (3-carboxypropyl) isocyanurate, 1,3-bis (2-carboxyethyl) isocyanurate These may be used alone or in combination of two or more. And it may be. Among these curing agents, phthalic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, dimethylglutaric anhydride, It is preferable to use diethylglutaric acid and 1,3,5-tris (3-carboxypropyl) isocyanurate. The curing agent (B) preferably has a molecular weight of about 100 to 400, and more preferably a colorless or pale yellow one.

  The mixing ratio of (A) the epoxy resin (or (G) oligomer) and (B) the curing agent is such that (A) 1 equivalent of epoxy group in the epoxy resin can react with the epoxy group (B). It is preferable that the ratio is such that the active group (acid anhydride group or hydroxyl group) in the curing agent is 0.5 to 0.7 equivalent, and 0.6 to 0.7 equivalent. Is more preferred. When the active group is less than 0.5 equivalent, the curing rate of the epoxy resin composition becomes slow, and the glass transition temperature of the obtained cured product becomes low, and a sufficient elastic modulus may not be obtained, On the other hand, when the above-mentioned active group exceeds 0.7 equivalents, the strength after curing may decrease (when the (G) oligomer is used alone or the (G) oligomer is used in combination with the (A) epoxy resin). The conversion of the equivalent number of (B) the curing agent in (A) is such that the total amount of the epoxy groups contained in each of the (A ′) epoxy resin and the (A) epoxy resin contained in the oligomer (G) is one equivalent, and B ′) The curing agent and (B) the total of active groups capable of reacting with the epoxy group contained in the curing agent are equivalent numbers.)

  The curing accelerator (C) is not particularly limited, and for example, 1,8-diaza-bicyclo (5,4,0) undecene-7, triethylenediamine, tri-2,4,6-dimethyl Tertiary amines such as aminomethylphenol, imidazoles such as 2-ethyl-4-methylimidazole and 2-methylimidazole, triphenylphosphine, tetraphenylphosphonium tetraphenylborate, tetra-n-butylphosphonium-o, o-diethyl Examples include phosphorus compounds such as phosphorodithioate, tetra-n-butylphosphonium-tetrafluoroborate and tetra-n-butylphosphonium-tetraphenylborate, quaternary ammonium salts, organic metal salts, and derivatives thereof. These may be used alone or in combination. Among these curing accelerators, tertiary amines, imidazoles, and phosphorus compounds are preferably used.

  The content of the curing accelerator (C) is preferably 0.01 to 8.0% by weight, more preferably 0.1 to 3.0% by weight, based on the epoxy resin (A). is there. When the content of the curing accelerator is less than 0.01% by weight, a sufficient curing promoting effect may not be obtained, and when the content exceeds 8.0% by weight, discoloration is observed in the obtained molded article. There is.

  The inorganic filler (D) is not particularly limited, and examples thereof include silica, alumina, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, magnesium carbonate, and barium carbonate. At least one member selected from the group consisting of silica, alumina, magnesium oxide, antimony oxide, titanium oxide, and zirconium oxide can be used from the viewpoint of heat conductivity, light reflection characteristics, moldability, and flame retardancy. , Aluminum hydroxide and magnesium hydroxide are preferred. The center particle size of the inorganic filler (D) is not particularly limited, but is preferably in the range of 1 to 100 μm so that packing with the white pigment is efficient.

  As the white pigment (E), known pigments can be used and are not particularly limited. For example, alumina, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide, inorganic hollow particles, and the like can be used. These may be used alone or in combination. Examples of the inorganic hollow particles include sodium silicate glass, aluminum silicate glass, sodium borosilicate glass, and shirasu. (E) The particle diameter of the white pigment preferably has a center particle diameter in the range of 0.1 to 50 μm. If the center particle size is less than 0.1 μm, the particles tend to aggregate and the dispersibility tends to be poor. If the center particle size exceeds 50 μm, the cured product may not have sufficient light reflection properties.

  The total blending amount of the (D) inorganic filler and the (E) white pigment is not particularly limited, but is preferably in a range of 10% by volume to 85% by volume based on the whole resin composition. If the total compounding amount is less than 10% by volume, the light reflection properties of the cured product may not be sufficiently obtained. If the total amount exceeds 85% by volume, the moldability of the resin composition deteriorates, and the substrate for mounting an optical semiconductor. Is difficult to fabricate.

  The (F) coupling agent is not particularly limited, but for example, a silane coupling agent or a titanate coupling agent can be used. As the silane coupling agent, for example, an epoxysilane-based or aminosilane-based coupling agent can be used. And cationic silanes, vinyl silanes, acryl silanes, mercapto silanes, and composites thereof. The type and processing conditions of (F) the coupling agent are not particularly limited, but the amount of the (F) coupling agent is preferably 5% by weight or less based on the resin composition.

  Further, to the thermosetting light reflecting resin composition of the present invention, (H) a thickener may be added for the purpose of adjusting the melt viscosity. (H) The thickener is not particularly limited, but for example, Leoloseal CP-102 sold by Tokuyama Corporation can be used. (H) The amount of the thickener to be added is preferably 0.15% by volume or less of the total volume of the resin composition. (H) If more than 0.15% by volume of the thickener is added, the fluidity of the resin composition at the time of melting is impaired, and sufficient material strength may not be obtained after curing. Further, (H) the thickener is preferably a nanoparticle filler having a center particle size of 1 nm to 1000 nm, and more preferably a nanoparticle filler having a center particle size of 10 nm to 1000 nm. . A filler having a center particle diameter smaller than 1 nm is not preferable in terms of characteristics because the particles tend to aggregate and the dispersibility tends to decrease. On the other hand, if a filler larger than 1000 nm is added, burrs tend not to be reduced, which is not preferable in terms of characteristics.

  Further, additives such as an antioxidant, a release agent, and an ion scavenger may be added to the resin composition of the present invention, if necessary.

  It is desirable that the thermosetting light-reflecting resin composition of the present invention containing the above components can be press-molded at room temperature (0 to 30 ° C.) before thermosetting, and after thermosetting. It is desired that the light reflectance at a wavelength of 350 nm to 800 nm is 80% or more. The above pressure molding may be performed, for example, at room temperature as long as the molding can be performed under the conditions of 5 to 50 MPa and about 1 to 5 seconds. On the other hand, if the light reflectance is less than 80%, there is a tendency that the brightness cannot be sufficiently improved in the optical semiconductor device. A more preferable light reflectance is 90% or more.

  Moreover, the thermosetting light-reflecting resin composition of the present invention can be obtained by uniformly dispersing and mixing the above-mentioned various components, and the means and conditions are not particularly limited, but as a general method, After sufficiently stirring and mixing components of a predetermined blending amount with a mixer or the like, kneading (melting) with a mixing roll, an extruder, a kneader, a roll, an extruder, etc., and further cooling and pulverizing can be mentioned. . The conditions for (melting) kneading may be appropriately determined depending on the types and amounts of the components, and are not particularly limited. However, it is preferable to perform (melting) kneading in a range of 15 to 100 ° C. for 5 to 40 minutes, and preferably 20 to 100 ° C. It is more preferable to knead (melt) for 10 to 30 minutes in the range described above. If the (melting) kneading temperature is lower than 15 ° C., it is difficult to knead (melt) each component, and the dispersibility tends to decrease. If the temperature is higher than 100 ° C., the resin composition has a high melting point. The molecular weight may progress and the resin composition may be cured. If the (melting) kneading time is less than 5 minutes, the generation of burrs tends to be unable to be effectively suppressed. If the kneading time is more than 40 minutes, the high molecular weight of the resin composition proceeds, The composition may be cured.

  In addition, the thermosetting light-reflecting resin composition of the present invention is preferably aged and left (aged) for the purpose of increasing the melt viscosity at the time of molding after compounding and kneading the above-mentioned components. Aging at -30 ° C. for 1-72 hours is more preferred, thermal aging at 15 ° C.-30 ° C. for 12-72 hours is more preferred, and thermal aging at 25 ° C.-30 ° C. for 24-72 hours. Is particularly preferred. When the aging is performed for a short time of less than 1 hour, the generation of burrs tends to be unable to be effectively suppressed. When the aging is performed for more than 72 hours, sufficient fluidity may not be ensured during transfer molding. When aging is performed at a temperature lower than 0 ° C., (C) the curing accelerator is inactivated, and the three-dimensional crosslinking reaction of the resin composition does not sufficiently proceed, and the viscosity at the time of melting may not increase. When the resin composition is aged at a temperature higher than 30 ° C., the resin composition absorbs moisture, and the mechanical properties such as the strength and elastic modulus of the cured product tend to deteriorate.

  The thermosetting light-reflecting resin composition of the present invention has a molding temperature of 100 ° C. to 200 ° C., a molding pressure of 20 MPa or less, and a burr length of 5 mm or less when subjected to transfer molding under the conditions of 60 to 120 seconds. Is preferred. More preferably, it is 3 mm or less, particularly preferably 1 mm or less. If the burr length is longer than 5 mm, the burr may protrude into the opening (recess) of the optical semiconductor element mounting area and may become an obstacle when mounting the optical semiconductor element, or a bonding wire may be formed between the optical semiconductor element and the metal wiring. For example, there is a possibility that it may become an obstacle when electrically connecting by a known method.

  The optical semiconductor element mounting substrate of the present invention is formed using the thermosetting light-reflecting resin composition of the present invention. For example, one or more concave portions serving as an optical semiconductor element mounting region are formed, At least the inner peripheral side surface of the concave portion is made of the thermosetting light reflecting resin composition of the present invention. One embodiment of the substrate for mounting an optical semiconductor element of the present invention is shown in FIG.

  The method for producing the substrate for mounting an optical semiconductor element of the present invention is not particularly limited. For example, the resin composition for thermosetting light reflection of the present invention can be formed by transfer molding. More specifically, for example, as shown in FIG. 2A, a metal wiring 105 is formed from a metal foil by a known method such as punching or etching, and then the metal wiring 105 is formed into a mold 301 having a predetermined shape. (FIG. 2 (b)), and the thermosetting light-reflecting resin composition of the present invention is injected from the resin injection port 300 of the mold 301, and this is preferably performed at a mold temperature of 170 to 200 ° C. and a molding pressure. After thermosetting at 0.5 to 20 MPa for 60 to 120 seconds and at an after-curing temperature of 120 ° C. to 180 ° C. for 1 to 3 hours, the mold 301 is removed and the cured thermosetting light reflecting resin composition is used. It can be manufactured by applying Ni / silver plating 104 by electroplating to a predetermined position of an optical semiconductor element mounting region (concave portion) 200 surrounded by a reflector 103 made of (FIG. 2C).

  Further, the optical semiconductor device of the present invention is provided with the optical semiconductor element mounting substrate of the present invention, an optical semiconductor element mounted on the bottom of the concave portion of the optical semiconductor element mounting substrate, and formed in the concave portion so as to cover the optical semiconductor element. And a phosphor-containing transparent sealing resin layer to be formed. In FIG. 3, an optical semiconductor element 100 is mounted at a predetermined position at the bottom of an optical semiconductor element mounting area (recess) 200 of an optical semiconductor element mounting substrate 110 of the present invention, and the optical semiconductor element 100 and metal wiring 105 are bonded. One of the optical semiconductor devices of the present invention in which the optical semiconductor element 100 is electrically connected by a known method such as a wire 102 or a solder bump 107 and the optical semiconductor element 100 is covered with a transparent sealing resin 101 including a known phosphor 106. 1 shows an embodiment.

  Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

<Preparation of thermosetting resin composition for light reflection>
(Examples 1 to 11, Comparative Examples 1 to 8)
After blending the respective materials according to the blending tables shown in Tables 1 and 2 and sufficiently kneading them by a mixer, they are melt-kneaded under predetermined conditions by a mixing roll, heat-aged if necessary, and cooled and pulverized. The thermosetting light-reflecting resin compositions of Examples 1 to 11 and Comparative Examples 1 to 8 were produced. In addition, the unit of the compounding amount of each component in the table is part by weight, and a blank column indicates no compounding or no process. Examples 1 to 5 are each a method using a specific (G) oligomer; (A) a range of 0.5 to 0.7 equivalent of an active group in a curing agent per 1 equivalent of an epoxy group in an epoxy resin. (H) a technique of adding a nanofiller as a thickener; a technique of heat-aging the composition under predetermined conditions; and a technique of adjusting the melt-kneading conditions (kneading time from 15 minutes to 30 minutes). Examples 6 to 11 are cases where any two of the above methods are used in combination. The oligomers used in Examples 1, 6, 7, and 9 were produced as described below, and had a viscosity at 100 ° C. of 1000 mPa · s.

(Method for producing oligomer)
The respective materials were blended according to the blending table shown in Table 1 (0.1 equivalent of acid anhydride group to 1 equivalent of epoxy group), melt-kneaded at 25 ° C. for 10 minutes with a mixing roll, and then the obtained clay-like mixture was obtained. The composition was heat aged at a temperature of 55 ° C. for 4 hours. Then, it was crushed using a ceramic mortar having a diameter of 300 mm until the particle diameter became 1 mm or less, and stored in an environment at a temperature of 0 ° C. or less.

<Evaluation of thermosetting resin composition for light reflection>
The resin compositions of Examples and Comparative Examples were evaluated by the following various property tests. The results are shown in Tables 1 and 2.

(Light reflectance)
The resin composition of each Example and each Comparative Example was transfer-molded under the conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a cure time of 90 seconds, and was post-cured at 150 ° C. for 2 hours to obtain a thickness of 1 A test piece of 0.0 mm was produced. Next, the light reflectance at a wavelength of 400 nm was measured using an integrating sphere spectrophotometer V-750 (manufactured by JASCO Corporation), and the light reflectance of each test piece was evaluated according to the following evaluation criteria.
Evaluation criteria ○: light reflectance of 80% or more at a light wavelength of 400 nm Δ: light reflectance of 70% or more and less than 80% at a light wavelength of 400 nm ×: light reflectance of less than 70% at a light wavelength of 400 nm

(Burr evaluation)
The light-reflective resin compositions of Examples and Comparative Examples were cast from a pot into a mold provided with slits having depths of 75, 50, 30, 20, 10, and 2 μm, respectively. Thereafter, the maximum value of the length of the resin burr generated by flowing in the gap between the upper die and the lower die of the molding die was obtained with a caliper. FIG. 4 is a schematic view of a mold for burr measurement and resin burr generated. In addition, the case where the maximum value of the burr length was less than 5 mm was good, and the case where it was 5 mm or more was NG. Table 1 shows the evaluation results. The evaluation criteria are as follows.
・ Evaluation criteria ◎: Burr length less than 3 mm ○: Burr length less than 5 mm ×: Maximum value of burr length is 5 mm or more

(Wire bonding)
Using the resin compositions of Examples and Comparative Examples, a substrate for mounting an optical semiconductor element was produced in accordance with the procedure of FIG. 2 under the same molding and curing conditions as those of a test piece produced for evaluating light reflectance. Next, after mounting the semiconductor element in the optical semiconductor element mounting area (recess) of the substrate, the wiring between the optical semiconductor element and the substrate is connected to a wire bonder (HW22U-H, manufactured by Kyushu Matsushita Electric Co., Ltd., trade name) with a diameter of 28 μm. The wire was wire-bonded and electrically connected. The substrate heating temperature during wire bonding was 180 ° C. Then, the tensile strength of the gold wire subjected to wire bonding was measured using a pull tester PTR-01 (trade name, manufactured by Resca Corporation), and the wire bonding property was evaluated according to the following evaluation criteria.
-Evaluation criteria ：: 10 g or more ：: 4 g or more and less than 10 g △: less than 4 g x: bonding not possible

* 1: Triglycidyl isocyanurate (epoxy equivalent: 100, manufactured by Nissan Chemical Industries, trade name: TEPIC-S)
* 2: Hexahydrophthalic anhydride (Wako Pure Chemical Industries, Ltd.)
* 3: Tetrahydrophthalic anhydride (Aldrich)
* 4: Methyl hexahydrophthalic anhydride (HN5500, manufactured by Hitachi Chemical Co., Ltd.)
* 5: PX-4ET, manufactured by Nippon Chemical Industry Co., Ltd.)
* 6: Trimethoxy epoxy silane (A-187, manufactured by Dow Corning Toray)
* 7: Fatty acid ester (manufactured by Clariant, trade name Hoechst Wax E)
* 8: Aliphatic ether (Toyo Petrolite Co., Ltd., product name: Unitox 420)
* 9: Fused silica (FB-301, manufactured by Denki Kagaku Kogyo Co., Ltd.)
* 10: Fused silica (FB-950, manufactured by Denki Kagaku Kogyo Co., Ltd.)
* 11: Fused silica (AD-25, manufactured by SO-25R)
* 12: Hollow particles (Sumitomo 3M, product name S60-HS)
* 13: Alumina (Amatex, AO-25R)
* 14: Nano silica (Tokuyama Corporation, trade name: Reolosil CP-102)

  As shown in Tables 1 and 2, the curable light-reflecting resin compositions of the examples have excellent light-reflecting properties, can suppress the occurrence of burrs due to transfer molding, and can improve wire bonding properties. It is possible. As a result, when an optical semiconductor element mounting substrate or an optical semiconductor device is manufactured using the curable light-reflecting resin composition of the present invention, a step of removing burrs is not required, and productivity such as cost and manufacturing time is reduced. It is very advantageous in terms of.

100 ····· Optical semiconductor element (LED element)
101 Transparent sealing resin 102 Bonding wire 103 Reflector 104 Ni / Ag plating 105 Metal wiring 106 Fluorescence Body 107: solder bump 110: optical semiconductor element mounting substrate 200: optical semiconductor element mounting area (recess)
300 resin injection port 301 mold 400 mold for burr measurement (upper mold)
401 ····· Die for measuring burr (lower mold)
402 resin inlet 403 cavity 404 slit (75 μm)
405 ····· Slit (50 μm)
406 ····· Slit (30μm)
407: Slit (20 μm)
408 ····· Slit (10 μm)
409 ... Slit (2μm)
410 ···· Resin burrs

Claims (16)

  (A ′) A thermosetting light reflecting resin composition comprising an oligomer of an epoxy resin and a (B ′) curing agent, and a white pigment.   The (A ′) epoxy resin contains at least one selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, diglycidyl isocyanurate, and triglycidyl isocyanurate. The thermosetting resin composition for light reflection according to claim 1.   The thermosetting light according to claim 1, wherein the (B ′) curing agent contains at least one selected from the group consisting of an acid anhydride curing agent, an isocyanuric acid derivative, and a phenolic curing agent. Reflective resin composition.   The white pigment according to any one of claims 1 to 3, wherein the white pigment contains at least one selected from the group consisting of alumina, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide, and inorganic hollow particles. Thermosetting resin composition for light reflection.   The mixing ratio of the (A ′) epoxy resin and the (B ′) curing agent is such that the epoxy group in the (A ′) epoxy resin is equivalent to 1 equivalent of the epoxy group and the (B ′) is capable of reacting with the epoxy group. The thermosetting light-reflecting resin composition according to any one of claims 1 to 4, wherein the ratio of the active groups in the curing agent is 0.3 equivalent or less.   The inorganic filler further comprises at least one selected from the group consisting of silica, aluminum hydroxide, magnesium hydroxide, barium sulfate, magnesium carbonate, and barium carbonate, according to any one of claims 1 to 5, The thermosetting resin composition for light reflection according to the above.   The thermosetting light-reflecting resin composition according to claim 6, wherein a total blending amount of the inorganic filler and the white pigment is in a range of 10% by volume to 85% by volume based on the whole resin composition. .   A thermosetting light-reflecting resin tablet, comprising the thermosetting light-reflecting resin composition according to claim 1.   The method for producing a thermosetting light-reflecting resin composition according to any one of claims 1 to 7, comprising a step of kneading (A ') an epoxy resin and (B') a curing agent to obtain an oligomer.   The method for producing a thermosetting light-reflecting resin composition according to claim 9, further comprising a step of aging the oligomer at a temperature of 25 to 60 ° C for 1 to 6 hours.   (A ′) A method for preserving an oligomer for a thermosetting light-reflecting resin composition obtained by kneading an epoxy resin and a (B ′) curing agent, wherein the oligomer is pulverized until the particle size becomes 1 mm or less, and the temperature is reduced. A storage method that stores in an environment of 0 ° C or less.   The method for producing a thermosetting light-reflecting resin composition according to any one of claims 1 to 7, wherein at least an oligomer and a white pigment are kneaded at a kneading temperature of 20 to 100 ° C and a kneading time of 10 to 30 minutes. A method for producing a thermosetting light-reflecting resin composition, comprising a step of forming a kneaded material by kneading under the following conditions.   The method for producing a thermosetting light-reflecting resin composition according to claim 12, further comprising a step of aging the kneaded material at 0 to 30 ° C for 1 to 72 hours.   8. An optical semiconductor device mounting substrate having at least one concave portion serving as an optical semiconductor element mounting region, wherein at least the inner peripheral side surface of the concave portion is the thermosetting resin according to claim 1. A substrate for mounting an optical semiconductor element, comprising a resin composition for light reflection.   A method for manufacturing an optical semiconductor element mounting substrate in which at least one concave portion serving as an optical semiconductor element mounting region is formed, wherein at least the concave portion is a light reflecting heat according to any one of claims 1 to 7. A method for producing a substrate for mounting an optical semiconductor, comprising a step of forming the substrate by transfer molding using a curable resin composition.   15. The substrate for mounting an optical semiconductor element according to claim 14, an optical semiconductor element mounted on a bottom surface of the concave part of the substrate for mounting an optical semiconductor element, and a phosphor formed in the concave part so as to cover the optical semiconductor element. An optical semiconductor device comprising at least a transparent sealing resin layer.